JP2014196494A - Ink compositions - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide nanoscale reinforcing fillers for compositions such as phase change inks.SOLUTION: A hydrophobically functionalized polyhedral oligomeric silsesquioxane as a reinforcing agent of an ink composition has the formula specified in the figure, where each R can be identical or different and independently represents a linear, branched or cyclic organic group selected from the group consisting of hydrophobic alkyl groups, hydrophobic aryl groups, hydrophobic arylalkyl groups, and hydrophobic cycloaliphatic groups, provided that at least one of the R groups is a wax-like aliphatic group.

Description

  This disclosure relates generally to nanostructured particles, methods of making and using such nanostructured particles. More particularly, this disclosure relates to nanostructured particles comprising polyhedral oligomeric silsesquioxanes that are self-assembled and functionalized hydrophobically or hydrophilically. Such particles are useful, for example, as nanoscale fillers for compositions such as inks, such as phase change ink compositions.

ＰＯＳＳ分子はそれ自体、８つのＲ基が約６未満の炭素の長さの有機基である場合（例えば、基がシクロペンチルなどの脂環式基、またはイソプロピルなどの６未満の炭素を有する直鎖アルキル基である場合）、約１〜３ｎｍの近似直径を有し、これにより、立方体シルセスキオキサンユニットは、ほとんど「球状」であるとみなすことができる。 There are several approaches on how to improve the robustness of solid inks. However, the correct solution has not been studied for inks, but can use new specialized material components that show hope when used in other composite materials and applications. An example of a material that provides such a possibility is the POSS polymer, which is known to form self-assembled nanostructures. POSS includes a Si ₈ O ₁₂ cage-like core and is surrounded by eight organic functional groups that can be varied in a structure represented by groups of the following structure (which can be the same or different): the has a cubic structure, polyhedral oligomeric silsesquioxane (P olypolyhedral O ligomeric S il s esquioxane), molecularly known as an exact organosilicon compound families:

A POSS molecule itself has eight R groups that are organic groups with a length of less than about 6 carbons (eg, an alicyclic group such as cyclopentyl or a straight chain with less than 6 carbons such as isopropyl. (When it is an alkyl group), it has an approximate diameter of about 1-3 nm, so that the cubic silsesquioxane unit can be considered almost “spherical”.

  POSS compounds are reportedly used to synthesize polymer nanocomposites that function to reinforce polymer binder materials such as epoxy resins, and in a manner similar to polymer-clay nanocomposites etc. Are known to provide enhanced reinforcing properties (see JD Richtenhan, supra). However, the disadvantages of using nanoclay materials as reinforcing fillers are challenges associated with the energy intensive top-down process required to disperse individual exfoliated clay layers or platelets within the polymer binder. Also, by using nanoscale material components such as POSS that can be dispersed at the molecular level, a self-assembly process to build a nanostructured layer that may serve as a reinforcing filler component for the binder material Can be used to create nanocomposites with enhanced mechanical properties. Many substituted POSS compounds with various organic R-groups and functional groups are commercially available from Hybrid Plastics Inc., some of which have been studied for various applications.

US Pat. No. 6,860,930 US Pat. No. 6,472,523 US Pat. No. 6,713,614

  There remains a need for specific components and / or composites that can be formulated into wax-based solid inks or other inks as reinforcing fillers that can improve the mechanical robustness of the ink.

  The present disclosure discloses nanostructured particles that can be used as nanoscale reinforcing fillers for compositions such as phase change inks, such as nanostructured self-assembled functionalized polyhedral oligomeric silsesquioxanes. These and other needs are addressed by providing structured particles.

FIG. 6 illustrates the formation of polybutadiene-POSS nanostructures. FIG. 5 shows that hydrophobically functionalized polyhedral oligomeric silsesquioxane self-assembles into a substantially layered nanostructure.

式において、Ｒ₁〜Ｒ₈基の各々は、同じかまたは異なるものとすることができ、独立して、有機アルキルまたはシクロアルキル基、例えば、１〜約５０の炭素原子、または約２〜約３０の炭素原子、または約４〜約１８の炭素原子を有する、例えば、置換または非置換脂肪族もしくは芳香族炭化水素基を示す。炭化水素基は環状、分枝または直鎖とすることができる。炭化水素基は飽和とすることができ、または不飽和を含んでもよい。炭化水素基は非置換とすることができ、またはハロゲン、メチル、エチル、イソブチル、イソオクチル、シクロペンチル、シクロヘキシル、ビニル、スチリル、トリメチルシロキシル、トリクロロシリルエチル、トリクロロシリルプロピル、ジクロロシリルエチル、クロロシリルエチル、フェニル、クロロベンジル、シアノエチル、シアノプロピル、ノルボルネニル、フルオロ、シラノール、ジメチルシラン、アルコキシ、メタクリレート、シラン、アニリン、アミン、フェノール、およびアルコールからなる群より選択される１つもしくは複数の基により置換することができる。ある実施形態では、炭化水素基は部分的にフッ素化され、または過フッ化される。 Embodiments of the present disclosure provide nanostructured particles comprising a hydrophobically functionalized polyhedral oligomeric silsesquioxane. Hydrophobically functionalized polyhedral oligomeric silsesquioxanes are generally represented by the following formula:

In the formula, each of the R _{1 to} R ₈ groups can be the same or different and independently represents an organic alkyl or cycloalkyl group, such as from 1 to about 50 carbon atoms, or from about 2 to about For example, it represents a substituted or unsubstituted aliphatic or aromatic hydrocarbon group having 30 carbon atoms, or from about 4 to about 18 carbon atoms. The hydrocarbon group can be cyclic, branched or straight chain. The hydrocarbon group can be saturated or may contain unsaturation. The hydrocarbon group can be unsubstituted or halogen, methyl, ethyl, isobutyl, isooctyl, cyclopentyl, cyclohexyl, vinyl, styryl, trimethylsiloxyl, trichlorosilylethyl, trichlorosilylpropyl, dichlorosilylethyl, chlorosilylethyl Substituted with one or more groups selected from the group consisting of phenyl, chlorobenzyl, cyanoethyl, cyanopropyl, norbornenyl, fluoro, silanol, dimethylsilane, alkoxy, methacrylate, silane, aniline, amine, phenol, and alcohol be able to. In certain embodiments, the hydrocarbon group is partially fluorinated or perfluorinated.

However, in order to provide a hydrophobically polyhedral oligomeric silsesquioxane is functionalized, at least one of R ₁ to R ₈ groups are waxy (waxy) aliphatic groups. The term “wax-like aliphatic group” means, for example, having at least 10 or at least 12 or at least 16 carbon atoms, for example from about 10 to about 100 or from about 12 to about 50 or from about 16 to about 40. Shows a hydrophobic long chain with carbon atoms. The waxy aliphatic group can be a saturated alkane hydrocarbon, for example, a poly (alkylene) wax such as polyethylene, polypropylene, or the like, or an unsaturated hydrocarbon such as polybutadiene, polyisoprene, or the like. Or any short saturated alkane group, straight chain, branched or containing cyclic group, such as hexadecyl, octadecyl, eicosanyl, docosanyl, tetracosanyl, hexacosanyl, octacosanyl, triacontanil, hexatriacontanyl, or longer As well as mixtures thereof. The waxy aliphatic group can also include a plurality of reactive functional groups for attachment to the POSS group. Examples of compounds having multiple reactive functional groups for attachment to POSS are C-36 dimer diol, C-36 dimer dibasic acid, or C-36 dimer diamine, which are Each is a commercially available waxy aliphatic compound available from UNIQEMA® that contains either two alcohols, carboxylic acids, or amino functions, and is produced by dimerization of oleic acid derivatives. The waxy aliphatic hydrocarbon can have 1 to about 10 reactive functional groups, such as 1 to about 6 reactive functional groups, or 1 to about 4 reactive functional groups. The reactive functional group R on the POSS molecule can be used for known grafting (covalent grafting) by chemical conversion or as a POSS polymer for polymerization. Are: halogens, primary or secondary hydroxyl, thiols, trialkoxysilyl, alkyldialkoxysilyl, dialkylalkoxysilyl, chlorodialkylsilyl, chlorodialkoxysilyl, dichloroalkylsilyl, trichlorosilyl, trivinylsilyl, Dialkylvinylsilyl, dialkylsilanyl, trialkylsilanol, primary or secondary alkoxyl, carboxylic acid or anhydride, alkoxycarbonyl ester, alkoxythiocarbonyl ester, thiol ester, primary or Are secondary amides, isosinato, isothiocyanato, nitrile, epoxy or oxirane groups such as glycidyl ethers, alkenyl groups and ethylenically unsaturated groups such as methacrylates, acrylates, vinyl ethers, terminal olefins such as allyl, norbornenyl, cyclohexenyl Or styryl, aldehyde or ketone, substituted amine, substituted imine, guanidino, substituted ammonium and / or phosphonium cation, carbamate or urethane, ureas, hydrazine, and semicarbazide.

  Wax-like aliphatic groups are desirably hydrophobic to polyhedral oligomeric silsesquioxane (POSS) groups or moieties. Thus, for example, since waxy aliphatic groups are more hydrophobic than POSS moieties, hydrophobically functionalized POSS compounds have a waxy aliphatic group that functions as a hydrophobic “tail” group. The POSS moiety functions as a polar “head” group. This bipolar functionality allows multiple hydrophobically functionalized POSS molecules to self-assemble as desired.

The ratio of POSS moiety to waxy aliphatic groups can be adjusted as desired. Thus, at least one of R ₁ to R ₈ groups are waxy aliphatic group, the ratio can be adjusted to provide some waxy aliphatic group substituted polyhedral oligomeric silsesquioxane compound Can do. In embodiments, the ratio of POSS moiety to waxy aliphatic group is, for example, from about 1: 1 (providing compounds wherein only one of the groups is a waxy aliphatic group) to about 1: 8 (R ₁ Provides compounds in which all or almost all of the R ₈ groups are waxy aliphatic groups). Thus, in embodiments, the ratio of POSS moiety to waxy aliphatic groups can be from about 1: 1 to about 1: 4 or about 1: 8, such as about 1: 1, 1: 2. In yet another embodiment, a hydrophobically functionalized dimer, for example, by using a waxy aliphatic group having two or more reactive functional groups for covalent attachment to the POSS moiety. Alternatively, multimeric polyhedral oligomeric silsesquioxane compounds can be formed. The ratio of POSS moieties to waxy aliphatic groups can be adjusted so that there are two or more POSS moieties attached to any one waxy aliphatic group, eg, waxy aliphatic A ratio of about 2: 1 can be obtained if the group is difunctional, or a ratio of about 3: 1 can be obtained if the waxy aliphatic group is trifunctional, and so on.

  The hydrophobically functionalized polyhedral oligomeric silsesquioxanes of the present disclosure can be readily prepared from commercially available materials using conventional chemical synthesis. For example, the synthesis includes commercially available polyhedral oligomeric silsesquioxane compounds, for example, at least one reactive functional group that can be readily converted to one or more waxy aliphatic chains by known chemical transformations. One can start with what is available from Hybrid Plastics (Hattysburg, Mississippi). For example, at least one reactive functional group on the polyhedral oligomeric silsesquioxane compound feedstock can be an ester, alcohol, amine, isocyanate, or as described in the embodiments. The reactive functional group can then be converted into suitable reagents such as saturated or unsaturated hydrocarbon monocarboxylic acids or dicarboxylic acids, saturated or unsaturated hydrocarbon esters or diesters, saturated or unsaturated hydrocarbon isocyanates or diisocyanates, saturated or unsaturated. Easily convert and expand to waxy aliphatic groups by reacting with hydrocarbon amines or diamines, saturated or unsaturated hydrocarbon alcohols or diols, or other reactive functional groups attached to saturated or unsaturated hydrocarbons can do.

Specific suitable examples of reagents that can be used include monofunctional waxes, such as (a) saturated hydrocarbon monocarboxylic acids having a carbon number (n) in the range of about 12 to about 100, such as , Hexadecanoic acid or palmitic acid, heptadecanoic acid, octadecanoic acid or stearic acid, eicosanoic acid or arachin (arachidone) acid, docosanoic acid or behenic acid, tetracosanoic acid or lignoceric acid, hexacosanoic acid or serotic acid, heptacosanoic acid, octacosanoic acid or montan Acid, triacontanoic acid, dotriacontanoic acid, tritriacontanoic acid, tetratriacontanoic acid, pentatriacontanoic acid, or a mixture of long chain saturated carboxylic acids, such as Baker Petrolite (Baker-) having more than 30 carbon atoms Petrolite) (B) unsaturated monocarboxylic acid waxes such as oleic acid, linoleic acid, erucic acid, etc .; (c) branched saturated or unsaturated monocarboxylic acid waxes such as A compound known as ISOCARB® 32 from Guerbet acid, isostearic acid, and Sasol North America (Houston, Tex.), Such as 2-decyltetradecanoic acid; (d) carbon atom Saturated hydrocarbon alcohols having a number (n) in the range of about 12 to about 100, such as dodecanol, tetradecanol, hexadecanol, octadecanol (also stearyl alcohol), isostearyl alcohol, eicosanol, docosanol, Tetracosanol and a UNILIN® mixture of linear primary alcohols with n = 24-50 carbon commercially available from Baker Petrolite (Sugar Land, Tex.) Or Sasol North America ( N> 20 saturated primary alcohol Alfol® blends commercially available from Houston, TX; (e) linear unsaturated primary alcohols such as hexadecenyl Alcohols, octadecenyl alcohol (oleyl alcohol), linoleyl alcohol, etc .; (f) branched saturated primary alcohols such as iso-stearyl alcohol or guerbet type alcohols such as 2-hexyldecanol, or iso-arachidyl Alcohol or 2-tetradec Octadecanol (available from Jarchem Industries, Newark, NJ), or the Isophor® series of branched primary alcohols available from Sasol North America (Houston, Texas); Alternatively, a C ₃₆ -dimer diol having 10,11-dioctyleicosanediol as a main component, such as a commercially available material such as Pripol 2003 or Pripol 2033 available from Uniqema (Newcastle, Delaware) Mixtures; (g) saturated hydrocarbon amines having from about 12 to about 100 carbon atoms (n) such as dodecylamine, octadecylamine (stearylamine) and similar aliphatic amines Or primary ether amines prepared from fatty alcohols and propylamine units, for example, tetradecyl-dodecyloxypropylamine, commercially available as PA-1816 (Tomah Products, Milton, Wis.); ) Branched saturated primary amines such as iso-stearyl amine or branched saturated ether amines such as 3-aminopropyl ether-functionalized molecular alcohols from Tomer Products (Milton, Wis.); And (i) above Other monofunctional carbons having the same hydrocarbon structure as listed in (a)-(h), wherein the functional group is a carboxylic acid derivative such as ester, amide, anhydride, urethane or carbamate, urea or isocyanate Hydrogen wax listed It is done.

Other examples of suitable reagents that can be used include bifunctional hydrocarbon waxes, such as (a) linear or branched dicarboxylic acids having a carbon number (n) in the range of about 12 to about 100. Acids such as 1,12-dodecanedioic acid, 1,15-pentadecanedioic acid, 1,18-octadecanedioic acid and 8-oxo-pentadecanedioic acid (available from Fulcrum Scientific, Huddersfield, UK) ), 1,18-octadecanedioic acid (available from TCI America Organic Chemicals, Portland, Oreg.), Docosanedioic acid (available from Aldrich, Milwaukee, Wis.) And commercially available preppo A C ₃₆ -dimer dibasic acid mixture based on 10,11-dioctyleicosane diacid as a main component, such as Cole 1006 or Pripol 1009 (available from Unikema, Newcastle, Delaware); and (b) carbon atoms Linear or branched primary diols having a number (n) in the range of about 12 to about 100, such as 1,18-octadecanediol or 1,18-octadec-9-ene-diol (respectively Jarchem) Mainly 10,11-dioctyl eicosandiol such as Pripol 2003 or Pripol 2033 available from Industries, Newark, NJ), or Pripol 2003 or Pripol 2033 available from Unikema (Newcastle, Delaware) As an ingredient, n = 36 Certain C ₃₆ -dimer diol mixtures; and (c) linear or branched primary diamines having a carbon number (n) in the range of about 12 to about 100, such as Henkel (currently Cognis (Cognis)) Basamin from (Versamine) 552 (saturated) or Basamin 551 (C _36, such as unsaturated) - dimer diamines, or Jeffamine polyether diamines based on polyethylene glycol backbone (JEFFAMINE) series ( Huntsman, available from Woodlands, Tex.); And any mixture of reagents listed above (a)-(c).

  As is apparent, although the range of suitable chemical functional groups on the polyhedral oligomeric silsesquioxane compound raw material is wide, the chemical functional groups in embodiments contain at least 12 carbons, such as from about 12 to about 100 carbon atoms. Optionally, it may contain one or more heteroatoms, for example O, N, S or P or halogen atoms.

  If desired or necessary, the reaction can be carried out in the presence of a catalyst. If a catalyst is used, any suitable catalyst can be used in known amounts. In general, when the catalyst is an acidic catalyst, it is desirable to use the POSS compound in an amount of 10 mol% or less based on the starting POSS material since it can be hydrolyzed by high levels of strong acid catalyst. However, when higher amounts of catalyst are used, the catalyst can be present in an amount of less than 50 mol% catalyst, for example less than 25 mol% catalyst. However, the amount of catalyst used can also be outside these ranges.

  In another embodiment, the functional group attached to the POSS compound is a hydrophilic group. Suitable hydrophilic groups include, for example, carboxylic acid and derivative groups, sulfonic acid and derivative groups, phosphoric acid and derivative groups and acid polar groups such as formyl groups; basic polar groups such as amino groups; and amide groups, esters And neutral polar groups such as groups, hydroxyl groups, alkoxyl groups, halo groups, and nitrile groups. Of course, other hydrophilic groups, as well as combinations thereof, can be used. Hydrophilic groups can be incorporated into the POSS structure in any suitable manner, generally using known chemical transformations.

  POSS is an organosilicate compound with a cage-like chemical structure that is assumed to be almost spherical and has a structure similar to a nonionic surfactant when functionalized with long aliphatic / hydrophobic carbon chains. These structural features of wax-functionalized POSS allow molecules to self-assemble into layered nanostructures, making it a good example of a class of highly ordered nanomaterials.

  The advantages of the hydrophobically functionalized polyhedral oligomeric silsesquioxanes of the present disclosure are readily self-assembled to about 1 to about 500 nm, such as about 1 to about 300 nm or about 1 to about 100 or about 200 nm. It can be a nanostructure, for example a substantially layered nanostructure, having dimensions in the range

  FIG. 2 shows that hydrophobically functionalized polyhedral oligomeric silsesquioxanes self-assemble into a substantially layered nanostructure. FIG. 2 shows the proposed nanostructured wax-functionalized POSS material. FIG. 2 also illustrates how this layered nanostructure interacts with a wax component in a composition such as a solid ink, where the wax component of the solid ink vehicle is Can occupy an interstitial space of the nanostructure in which a hydrophobic alkyl chain is present.

  Based on the small angle X-ray scattering (SAXS) data measured by Zheng et al. Cited above, the nanostructure constructed from PBD-functionalized POSS has a hydrophobically functionalized polyhedral oligomeric silsesquioxy of the present disclosure. The distance between layered sheets formed from suns is expected to be in the range of 10-20 nm. Thus, in embodiments, the distance between the layered sheets can be from about 1 to about 100 nm, such as from about 2 to about 80 nm or from about 10 to about 50 nm.

  The lateral dimensions of the nanostructures, as well as the possible stacking of layered sheets in one array, can be controlled by the weight percent loading of wax-modified POSS particles in the desired composition, such as a wax-based ink vehicle. In embodiments, the loading of wax-modified POSS particles in the desired composition can be from about 1 wt% or less to about 50 wt% or more. In some applications, such as solid ink vehicles, the wax-modified POSS particles can be present in a loading range of about 1 to about 50 wt%, such as about 25 wt% or less in the ink, or about 15 wt% or less in the ink.

  The formed layered nanostructure can be used, for example, as a toughening agent in various compositions, such as liquid ink vehicles. For example, formulating hydrophobically functionalized POSS nanoparticles to form a “low energy” solid ink or phase change ink, solvent-based liquid ink or alkyloxylated monomer having a melting point in the range of about 60 ° C. to about 130 ° C. It can be a variety of ink vehicles, including radiation curable liquid inks composed of the like, and even aqueous inks. For end use in piezoelectric inkjet printing, nano-sized pigment particles are advantageous to ensure reliable inkjet printing and to prevent jet inhibition due to pigment particle aggregation.

  Inkjet ink compositions according to this disclosure generally comprise a carrier, a colorant, and one or more additives. Examples of such additives include solvents, waxes, functional resins, particle dispersants, antioxidants, tackifiers, slip aids, curable properties, and the like. Examples include curable components such as monomers and / or polymers, gelling agents, initiators, sensitizers, humectants, biocides, preservatives, and the like. The formed layered nanostructure can be used, for example, as a reinforcing agent in such inks. The strengthening action of POSS nanostructures can be further enhanced by the use of organic gelling agents or gelling agent components, which can help align or co-crystallize POSS nanostructured particles. It acts to form a crystallized 2-dimensional network in the carrier.

  The ink composition also includes a carrier material, or a mixture of two or more carrier materials. The carrier material can vary, for example, depending on the particular type of ink composition. In the case of a solid (or phase change) inkjet ink composition, the carrier can include one or more organic compounds. Carriers for such solid ink compositions are typically solid at room temperature (about 20 ° C. to about 25 ° C.), but phase change at the printer operating temperature required to be jetted onto the print surface. The operating temperature can be between about 60 ° C. and about 140 ° C., but can be outside that range. The ink carrier disclosed herein can include a low melting wax, which can include a polyalkylene wax, such as polyethylene wax or polypropylene wax, or mixtures thereof. The polyalkylene wax (es) can be present in any desired or effective amount in the ink carrier, and in one embodiment at least 25% by weight of the ink carrier, in another embodiment, at least 30% of the ink carrier. %, In another embodiment, at least about 35% by weight of the ink carrier, and in one embodiment no more than about 65% by weight of the ink carrier, in another embodiment no more than about 55% by weight of the ink carrier, In embodiments, it can be present in an amount up to about 50% by weight of the ink carrier.

  Additional suitable solid ink carrier materials include paraffins, microcrystalline waxes, ester waxes, amide waxes, fatty acids, fatty alcohols, fatty amides and other waxes (Wax) -like materials, sulfonamide materials, resinous materials made from different natural sources (such as tall oil rosins and rosin esters), and many synthetic resins, oligomers, polymers and copolymers For example, ethylene / vinyl acetate copolymers, ethylene / acrylic acid copolymers, ethylene / vinyl acetate / acrylic acid copolymers, copolymers of acrylic acid and polyamides, ionomers, and the like, and mixtures thereof. One or more of these materials can also be used in a mixture with a fatty amide material and / or an isocyanate-derived material. Further, these waxes can be used in addition to the formed layered nanostructure, if desired.

Suitable carrier materials for solid ink compositions can also thus include, for example, amides, which include diamides, triamides, tetraamides, and the like. In embodiments where amide is used as the carrier material, triamide is particularly useful. This is because triamides are considered to have a structure that is more three-dimensional than other amides such as diamides and tetraamides. For example, the ink carrier may include a branched tetraamide, where n is an integer greater than or equal to 39 and less than 99, where R ₁ and R ₂ each include at least one carbon unit.

  The ink carrier may also include a branched triamide, where n has an average value between about 34 and 40, where x, y, and z can each be 0 or an integer, Here, the sum of x, y, and z is about 5 or more and 6 or less.

  The ink carrier may also include a gelling agent, which can be a crystalline or semi-crystalline material. Suitable examples of gelling agents for use in the ink carrier of the phase change ink composition include, but are not limited to, ester-terminated amide gelling agents, as well as ester-amide gelling agents. These ester-amide gelling agents can be present in the ink carrier in any desired or effective amount, ranging from about 0.5% to about 30% by weight of the ink carrier.

  Other gelling agents suitable for use in the phase change ink composition include urea or urethane type gelling agents such as N, N-dialkylurea compounds or N, O-dialkylcarbamate compounds, or urea-urethane compounds. And dimeric urea-urethane compounds including trans-1,2-cyclohexanebis [urea-urethane] compounds, or compounds thereof.

式において、Ｒ₁およびＲ₁'はそれぞれ、もう一方とは独立して、アルキレン基、アリーレン基、アリールアルキレン基、またはアルキルアリーレン基であり、Ｒ₂およびＲ₂'はそれぞれ、もう一方とは独立して、アルキル基、アリール基、アリールアルキル基、またはアルキルアリール基であり、Ｒ₃およびＲ₃'はそれぞれ、もう一方とは独立して、水素原子またはアルキル基であり、Ｒ₄およびＲ₄'はそれぞれ、もう一方とは独立して、水素原子、フッ素原子、アルキル基、またはフェニル基であり、ｎは０、１、２、３、または４の整数であり、Ｒ₅はアルキル基、アリール基、アリールアルキル基、アルキルアリール基、またはアルキル、アリール、アリールアルキル、またはアルキルアリール基以外の置換基である。

In the formula, R ₁ and R ₁ ′ are each independently an alkylene group, an arylene group, an arylalkylene group, or an alkylarylene group, and R ₂ and R ₂ ′ are each independently of the other Independently an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, wherein R ₃ and R ₃ ′ are each independently a hydrogen atom or an alkyl group, and R ₄ and R 3 Each ₄ ′ independently of the other is a hydrogen atom, a fluorine atom, an alkyl group, or a phenyl group, n is an integer of 0, 1, 2, 3, or 4, and R ₅ is an alkyl group , Aryl groups, arylalkyl groups, alkylaryl groups, or substituents other than alkyl, aryl, arylalkyl, or alkylaryl groups.

式において、Ｒ₁およびＲ₁'はそれぞれ、もう一方とは独立して、アルキル基、アリール基、アリールアルキル基、またはアルキルアリーレン基であり、Ｒ₂およびＲ₂'はそれぞれ、もう一方とは独立して、アルキレン基、アリーレン基、アリールアルキレン基、またはアルキルアリーレン基であり、Ｒ₃はアルキレン基、アリーレン基、アリールアルキレン基、またはアルキルアリーレン基であり、Ｒ₄およびＲ₅はそれぞれ、もう一方とは独立して、水素原子またはアルキル基である。

In the formula, R ₁ and R ₁ ′ are each independently an alkyl group, an aryl group, an arylalkyl group, or an alkylarylene group, and R ₂ and R ₂ ′ are each independently of the other Independently, an alkylene group, an arylene group, an arylalkylene group, or an alkylarylene group, R ₃ is an alkylene group, an arylene group, an arylalkylene group, or an alkylarylene group, and R ₄ and R ₅ are each Independently of one, it is a hydrogen atom or an alkyl group.

式において、Ｒ₁およびＲ₂はそれぞれ、もう一方とは独立して、（ｉ）直鎖、分枝、飽和、不飽和、環状、置換、および非置換アルキル基を含むアルキル基であり、ここで、酸素、窒素、硫黄、ケイ素、リン、ホウ素などのヘテロ原子がアルキル基中に存在してもよく、または存在しなくてもよく、少なくとも４つの炭素原子、かつ約６０以下の炭素原子を有する。

Wherein R ₁ and R ₂ are each independently of one another (i) an alkyl group including straight chain, branched, saturated, unsaturated, cyclic, substituted, and unsubstituted alkyl groups, wherein And heteroatoms such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron may or may not be present in the alkyl group, and contain at least 4 carbon atoms and up to about 60 carbon atoms or less. Have.

  The gelling agent can have a melting point of at least about 60 ° C and no more than about 160 ° C. The gelling agent is present in the ink carrier in any desired or effective amount, ranging from at least about 0.5 wt% to about 30 wt%.

  The ink carrier in the solid ink composition can be present in the ink in any desired or effective amount. For example, the carrier can be present in an amount of about 0.1 to about 99%, such as about 50 to about 98%, or about 90 to about 95% by weight of the ink.

  The ink composition can also contain a viscosity modifier as required. When present, the viscosity modifier used as needed is any desired or effective amount in the ink, such as from about 0.1 to about 99% by weight of the ink, such as from about 1 to about 30%, or It can be present in an amount of about 10 to about 15% by weight.

  In general, the ink composition includes one or more colorants. Any desired or effective colorant can be used in the ink composition, including pigments, dyes, pigment-dye mixtures, pigment mixtures, dye mixtures, and the like.

  The colorant can be present in the ink composition in any desired or effective amount to obtain the desired color or hue. For example, the colorant is typically at least about 0.1% by weight of the ink, such as at least about 0.2% or at least about 0.5%, and typically not more than about 50%, for example, It can be present in an amount up to about 20% by weight or up to about 10% by weight.

  The ink composition can also optionally contain an antioxidant. Antioxidants used as needed in the ink composition protect the image from oxidation and protect the ink components from being oxidized during the heated portion of the ink preparation process. When present, the optional antioxidant is used in the ink in any desired or effective amount, such as at least about 0.01 to about 20%, such as about 0.1 to about 5% by weight of the ink. Or from about 1 to about 3% by weight.

  Examples of other additives used for the ink include a clarifying agent, a tackifier, and an adhesive. Such additives can be included in conventional amounts for their normal purposes.

In order to disperse and stabilize the wax-functionalized POSS nanostructures, or pigment particles (if present) or other nanoparticles present in the ink vehicle, the particle dispersant is in any desired or effective amount in the ink. Can exist. The dispersant is present in any desired or effective amount ranging from at least 1 × 10 ⁻³ wt% of the ink carrier and up to about 30 wt% of the ink carrier.

  Rosin ester resins, mixtures thereof, and the like can also be included in the ink carrier. The rosin ester resin can be in any desired or effective amount in the ink carrier, in one embodiment at least about 0.5% by weight of the ink carrier, in another embodiment, at least about 2%, and yet another implementation. The form is present in an amount of at least about 3% by weight, and in one embodiment no more than about 20% by weight, in another embodiment no more than about 15% by weight, and in yet another embodiment an amount of about 10% by weight.

  Solid or phase change ink compositions typically have a melting point of about 50 ° C. or higher, such as about 50 ° C. to about 160 ° C. or higher. In embodiments, the ink composition has a melting point of about 70 ° C to about 140 ° C, such as about 80 ° C to about 100 ° C. The ink composition is also typically at a jetting temperature (eg, typically from about 75 ° C to about 180 ° C, or from about 100 ° C to about 150 ° C or from about 120 ° C to about 130 ° C), typically from about 2 to about It has a melt viscosity of 30 centipoise, such as from about 5 to about 20 centipoise or from about 7 to about 15 centipoise. Because image hardness tends to decrease with decreasing viscosity, in embodiments it is desirable to keep the viscosity as low as possible and still maintain the desired degree of image hardness.

  The ink compositions of the present disclosure can also include other materials as needed, which can depend on the type of printer in which the ink is used. For example, the carrier composition is typically designed for use in either a direct printing mode or an indirect or offset printing transfer system.

  In another embodiment comprising non-aqueous inks, solvent-based inks, such as petroleum-based inks, environment, which can include wax-functionalized POSS nanoparticles, aliphatic hydrocarbons, aromatic hydrocarbons, and mixtures thereof It can be used in soy and vegetable oil based inks, linseed oil based inks and other inks based on vehicles derived from natural sources. Other examples of ink vehicles for wax-functionalized POSS nanoparticles include alkyd isophthalates, higher alcohols, and the like. In yet another embodiment, the present invention of wax-functionalized POSS nanoparticles can be applied to relief printing, gravure, stencil, and inks used in lithographic printing.

  The ink compositions of the present disclosure can be prepared by any desired or suitable method. For example, in the case of a solid or phase change ink, the ink components are mixed together and subsequently heated to a temperature typically from about 100 to about 140 ° C. and stirred until a homogeneous ink composition is obtained, followed by the ink. Can be allowed to cool to ambient temperature (typically about 20 to about 25 ° C.). In the case of liquid ink compositions, the ink components can be simply mixed with stirring to provide a homogeneous composition, but heated if desired or necessary to help form the composition. You can also.

  Nanoparticles in embodiments herein can be dispersed in a solvent, such as a low boiling solvent, and then transferred from the solvent phase to the ink vehicle where the ink carrier and low energy phase change. Spreads uniformly in the ink. The solvent can be an organic solvent in one embodiment, and can be a low boiling point organic solvent in another embodiment. These solvents in one embodiment have a boiling point of 140 ° C. or lower, in another embodiment, have a boiling point of about 130 ° C. or lower, and in yet another embodiment, have a boiling point of about 120 ° C. or lower. In one embodiment, the loading of the wax-functionalized POSS nanoparticles into the solvent is at least about 10%, in another embodiment at least 20%, and in yet another embodiment at least about 30%; In one embodiment, no more than about 60%, in another embodiment no more than about 50%, and in yet another embodiment no more than about 45%, all of which are weight percent.

  The inks disclosed herein can be obtained by dispersing the wax-functionalized POSS nanoparticle dispersion in the ink component in a manner that maximizes uniform dispersion and resists agglomeration. For example, a method for producing a low energy phase change ink composition comprises a colloidal dispersion of wax-functionalized POSS nanoparticles in a solvent, a low melting point wax, and optionally a gelling agent. The step of mixing together the containing ink carrier can be included. The ink carrier exhibits a substantially uniform distribution of nanoparticles discretely distributed therein and a substantially increased resistance to aggregation of the nanoparticles distributed therein. The method involves substantially evaporating the solvent while mixing the low melting wax and other components of the ink carrier, such as a gelling agent, particle dispersant, resin, etc., with the wax-functionalized POSS nanoparticles in the solvent. Forming a homogeneous ink carrier solution. Thereafter, a colorant is added to the substantially homogeneous ink carrier solution to form a low energy phase change ink composition.

Example 1.
To 50 mL of toluene, [ethyl undecanoate] -isobutyl-POSS (from hybrid plastic, 2.0 mmol, 2.06 g), stearyl alcohol (4.0 mmol, 1.08 g), and para-toluenesulfonic acid as a catalyst (0.20 mmol, 0.04 g) was added and heated to reflux for about 5 hours. The mixture was then cooled to room temperature, extracted into 100 mL of ethyl acetate and washed with dilute sodium bicarbonate solution (10% NaHCO ₃ ). The ethyl acetate extract was dried over anhydrous sodium sulfate, filtered and concentrated to give a clear waxy semi-solid in quantitative yield. Product formation was confirmed by ¹ H-NMR spectroscopy. The reaction scheme is shown below.

Example 2
[Ethylundecanoate] -isobutyl-POSS (4.12 g, 4.0 mmol from hybrid plastic) and 36-carbon dimer diol (2.0 mmol, 1.0 g) known as Pripol 2003 purchased from Unikema And para-toluenesulfonic acid (0.2 mmol, 0.04 g) as a catalyst was added to 30 mL of toluene, and the mixture was heated to reflux for about 5 hours. The dark brown solution mixture was then cooled, extracted into 150 mL of ethyl acetate, washed several times with deionized water to remove the acid catalyst, and then washed with brine until the pH was neutral. The ethyl acetate extract was dried over anhydrous magnesium sulfate, filtered and concentrated to give a dark yellow semi-solid paste in quantitative yield. ^{By 1} H-NMR spectroscopy, the structure of the crude product was determined as a mixture of monoester and diester products with no unreacted starting material. The reaction scheme is shown below.

Example 3
To 30 mL of toluene, [ethyl undecanoate] -isobutyl-POSS (4.0 mmol, 4.12 g from hybrid plastic), 1,12-dodecanediol (2.0 mmol, 0.40 g), and para -A mixture with toluenesulfonic acid (0.10 mmol, 0.02 g) was added and heated to reflux for about 8 hours. The mixture was then cooled to room temperature, diluted with 30 mL of ethyl acetate, washed with deionized water to remove the acid catalyst, and then washed with brine. The ethyl acetate extract was dried over anhydrous magnesium sulfate, filtered and concentrated to give a clear solid in quantitative yield. The formation of the product was confirmed by ¹ H-NMR spectroscopy. The reaction scheme is shown below.

Example 4
To 50 mL of toluene, [1,2-propanediol] -isobutyl-POSS (from hybrid plastic, 1.9 g, 2.0 mmol), stearic acid (4.5 mmol, 1.28 g) and para-toluene as catalyst Add a mixture with sulfonic acid (0.20 mmol, 0.04 g) and heat to reflux for about 5 hours. The mixture is cooled and extracted into 100 mL of ethyl acetate, washed with deionized water followed by dilute sodium bicarbonate solution (10% NaHCO ₃ ) and finally with brine. The ethyl acetate extract is dried over anhydrous magnesium sulfate, filtered and concentrated to give a waxy semi-solid in quantitative yield. The reaction scheme is shown below.

Example 5 FIG.
A solution containing [3-aminopropyl] -isobutyl-POSS (from hybrid plastic, 2.0 mmol, 1.75 g) dissolved in 30 mL of anhydrous toluene is stirred under an inert atmosphere. A second solution containing stearyl isocyanate (2.1 mmol, 0.62 g) dissolved in 15 ml of anhydrous toluene is slowly added dropwise to the room temperature POSS solution, and then the resulting mixture is allowed to stir at room temperature for an additional 2 hours. When the solvent is removed from the crude reaction mixture by vacuum distillation, a waxy semi-solid is obtained in quantitative yield. The reaction scheme is shown below.

Example 6
Several phase change / solid ink compositions are disclosed that include wax-modified POSS nanoparticles with a loading in the range of 2 wt% to about 20 wt%. Three examples are provided that are only low energy / low melt solid ink vehicles, ie, no colorants and other ink components. One example includes about 2 wt% octaisodecyl POSS nanoparticles, another example about 5 wt% octaisodecyl POSS nanoparticles, and yet another particle about 10 wt% wax-modified nanoparticles from Example 1. Although two cyan colored solid ink examples are described, one example includes about 10 wt% POSS particles from Example 1, and another example includes about 5 wt% POSS particles from Example 1. An example of a yellow colored solid ink containing about 10 wt% octaisobutyl POSS will be described.

Ink vehicle examples
2.66 g (46.57 wt%) and 30 hydrocarbon average of 2 wt% polyethylene wax (PE500, Baker Petrolite, available from Tulsa, Oklahoma, polyethylene wax with an average chain length of 36 hydrocarbons) Add 2 wt% octaisobutyl POSS particles by adding 5.14 g (51.43 wt%) of Unilin® 425 with chain length (Baker Petrolite, available from Tulsa, Oklahoma) to the beaker A phase change solid ink vehicle was prepared. The materials were melted together in a heated reaction block at a temperature of about 110 ° C. and stirred at 500 rpm for 0.5 hour. To this mixture was then added 0.2 g (2 wt%) octaisobutyl-POSS (available from Aldrich Fine Chemicals) and the temperature was raised to 120 ° C. The mixture was stirred for an additional hour and then cooled to room temperature.

Ink vehicle example 2
A phase change solid ink vehicle containing 5 wt% octaisobutyl-POSS was prepared as in Ink Vehicle Example 1 except that the temperature was raised to 140 ° C. after adding POSS. The vehicle thus prepared exhibited a viscosity of 8.3 centipoise when measured at 110 ° C. with an RFS3 Rheometrics parallel plate viscometer.

Ink vehicle example 3.
A 10 wt% phase change solid ink vehicle comprising wax modified POSS from Example 1 is prepared as described for Ink Vehicle Example 2.

  Even when POSS particles were added to the ink vehicle, the viscosity did not increase significantly (only 1.15 cps increased after the addition of 5 wt% POSS particles). This shows well that the ink can withstand higher loads of POSS nanoparticles to improve the robustness.

（ｄ）ナウガード（ＮＡＵＧＵＡＲＤ）（登録商標）４４５抗酸化剤（ユニロイヤルケミカル社（Ｕｎｉｒｏｙａｌ Ｃｈｅｍｉｃａｌ Ｃｏ．）、コネチカット州ミドルベリー）０．１７ｇ、（ｅ）米国特許第６，８６０，９３０号（この開示内容は参照により本明細書に全体として含まれる）で記述されているトリアミド樹脂２．１８ｇ；（２）（１）で得られた分散物をさらに２時間撹拌する；（３）温度を約１００℃まで上昇させ、トルエン溶媒を、粘性溶液が得られるまで、徐々に蒸発させる；（４）粘性溶液の温度を約１３５℃までさらに上昇させ、インク成分の溶解／溶融を容易にする；（５）透明で均質な溶液が得られ、トルエン全てがインクから除去されるまで、温度を１３５℃で維持する；（６）ポリエチレンワックス（ＰＥ５００、ベイカーペトロライト、オクラホマ州タルサから）５０．１３ｇを熱分散物に徐々に添加し、分散物をさらに２時間約５００ｒｐｍで撹拌した；（７）米国特許第６，４７２，５２３号の実施例ＶＩＩＩで開示したシアン着色剤３．４７ｇを添加し、インクをさらに約２時間１３５℃で撹拌し、その後、室温まで冷却させる。 Ink Example 1
A cyan ink composition is prepared as follows: (1) A dispersion of wax-modified POSS particles from Example 2 (40% toluene dispersion) with mixing in a beaker at a temperature in the range of 40-70 ° C. To 16.25 g, components (a)-(e) are added: (a) Unilin® 425 (from Baker Petrolite, Tulsa, Oklahoma) (Class long chain alcohol) 55.38 g, (b) glycerol ester of hydrogenated rosin acid (KE-100, Arakawa Chemical Industries, Ltd., Osaka, Japan) 7.09 g, (c) alkylbenzyl phthalate of the following formula ( SANTICIZER (R) 278, Ferro Corporation, from Bridgeport, NJ) 5.08 g:

(D) NAUGUARD (R) 445 antioxidant (Uniroyal Chemical Co., Middlebury, Conn.) 0.17g, (e) U.S. Patent No. 6,860,930 (this 2.18 g of the triamide resin described in the disclosure is incorporated herein by reference in its entirety; (2) the dispersion obtained in (1) is stirred for an additional 2 hours; (3) the temperature is about Raise to 100 ° C. and allow the toluene solvent to evaporate gradually until a viscous solution is obtained; (4) further increase the temperature of the viscous solution to about 135 ° C. to facilitate dissolution / melting of the ink components; 5) A clear and homogeneous solution is obtained and the temperature is maintained at 135 ° C. until all of the toluene is removed from the ink; (6) Polyethylene wax ( 50.13 g (from E500, Baker Petrolite, Tulsa, Oklahoma) was slowly added to the heat dispersion and the dispersion was stirred for another 2 hours at about 500 rpm; (7) Implementation of US Pat. No. 6,472,523 3.47 g of the cyan colorant disclosed in Example VIII is added and the ink is stirred for an additional 2 hours at 135 ° C. and then allowed to cool to room temperature.

Ink Example 2
A cyan phase change solid ink is prepared as described in Ink Example 1 except that 10 wt% of the wax modified POSS from Example 1 is used.

Ink Example 3
A yellow phase change solid ink is prepared as described in Ink Example 1 except that 10 wt% of octaisobutyl POSS and the yellow colorant described in US Pat. No. 6,713,614 are used.

[Appendix]
(1) The equivalent ratio of the polyhedral oligomeric silsesquioxane raw material compound to the reagent is about 1: 1 to about 1: 3.

  (2) The carrier is present in an amount of about 50 to about 99.9% by weight, the colorant is present in an amount of about 0.1 to about 50% by weight of the ink, and the toughening agent is about 1 to about 1% of the ink. An ink composition present in an amount of about 50% by weight;

  (3) Surfactant, light stabilizer, UV absorber, fluorescent whitening agent, thixotropic agent, dewetting agent, slip agent, foaming agent, antifoaming agent, fluidizing agent, oil, plasticizer, Further comprising at least one additive selected from the group consisting of binders, conductive agents, fungicides, bactericides, organic and inorganic filler particles, leveling agents, opacifiers, antistatic agents, dispersants, and mixtures thereof. Ink composition.

Claims (4)

A carrier containing waxes;
A colorant;
As a toughener, a hydrophobically functionalized polyhedral oligomeric silsesquioxane, and
Including
Hydrophobically functionalized polyhedral oligomeric silsesquioxane interacts with the waxes contained in the carrier to self-assemble into a layered nanostructure, and the waxes contained in the carrier occupy a layered interstitial space. An ink composition characterized by the above. The ink composition according to claim 1, wherein the polyhedral oligomeric silsesquioxane is:
An ink composition having the following formula:

(In the formula, each R may be the same or different and is independently selected from the group consisting of a hydrophobic alkyl group, a hydrophobic aryl group, a hydrophobic arylalkyl group, and a hydrophobic alicyclic group. Represents a linear, branched or cyclic organic group,
Provided that at least one of the R groups is a wax-like aliphatic group) The ink composition according to claim 1,
An ink composition having a distance between layered sheets of 1 nm to 100 nm. The ink composition according to claim 1,
An ink composition comprising polyhedral oligomeric silsesquioxane in an amount of 1 to 15% by weight in the ink.

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